Exhaust gas sensor

ABSTRACT

An exhaust gas sensor in which a metal oxide semiconductor containing at least one member of a group of elements consisting of Sn, Fe, Ni and Co and Pt electrodes having ZrO 2 , deposited in the grain boundary are used. Such metal oxide semiconductors include, for example, SnO 2 , BaSnO 2 , BaSnO 3 , SrSnO 3 , and CaSnO 3 . The exhaust gas sensors are manufactured by mixing such compounds as BaCO 3 , SrCO 3  or CaCO 3  with SnO 2  in equimolar ratio to react them in air at 1200° C. for four hours. The compounds thus obtained were pulverized and Pt electrodes with ZrO 2  were imbedded therein, then were molded into sensor chips. The chips thus molded were baked by heating in air. After the chip has been sintered the exhaust gas sensor was assembled. It comprised an insulating substrate of alumina, etc. having a recess provided at one end thereof in which the aforementioned sensor chip was housed. The electrodes on the chip were housed in grooves provided in the substrate with their ends connected with base metal outside leads. Then an alumina sheet was pasted on the substrate, leaving a gap along the circumferential rim of the chip, thereby shielding and protecting the electrode from the atmosphere.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an improvement in exhaust gas sensors utilizing a change in resistance value of metal oxide semiconductors, and more particularly to an improvement in durability of electrodes. The exhaust gas sensor of the invention is suitable for detection of the air-fuel ratio in automobile engines, space heaters or boilers, etc.

2. Prior Art

Hitherto, a problem that Pt electrodes of an exhaust gas sensor are corroded by high temperature reducing atmosphere has been well known. For example, U.S. Pat. No. 4,237,722 proposes the use of a Pt-Rh alloy as highly durable electrodes, disclosing that such corrosion is caused by reaction of Pt with carbon in the exhaust gases.

The inventors' tests confirmed that the Pt-Rh alloy had excellent durability, when TiO₂ was used as a metal oxide semiconductor (Table 2), but the situation is quite different with compounds containing an Sn compound such as SnO₂, BaSnO₃, etc. When the Pt-Rh alloy electrodes are used with these compounds, the electrodes are corroded in high temperature reducing atmospheres. The Pt-Rh alloy electrodes are effective with TiO₂, but are ineffective with BaSnO₃ or SnO₂, etc. Elementary analysis of corroded electrodes revealed the formation of solid solutions of Pt and Sn. The cause of corrosion is not the reaction of Pt with carbon, but the formation of an alloy of Pt and Sn.

The inventors further found that Pt-Rh electrodes were corroded by metal oxide semiconductors, including Fe, Ni, or Co elements, because of the alloy formation with Pt. When these elements are used, the electrodes are corroded in a high temperature reducing atmosphere. Main materials of exhaust gas sensors containing these elements include such perovskite compounds as SrFeO₃, LaNiO₃ and LaCoO₃, etc.

According to related prior arts, TiO₂ is a representative exhaust gas sensor material and its characteristics are described in U.S. Pat. No. 3,886,785, etc. SrFeO₃, LaNiO₃ and LaCoO₃ are p-type metal oxide semiconductors and their resistance values diminish with oxygen concentrations and increase with combustible gas concentrations. These compounds all have crystalline structure of perovskite type, and characteristics of SrFeO₃ are described, for example, in U.S. Pat. No. 3,558,280, while those of LaCoO₃ and LaNiO₃, for example, in "Proceedings of the International Meeting on Chemical Sensors" (Kodansha 1983) and U.S. Pat. No. 4,507,643, etc. SnO₂ is an n-type metal oxide semiconductor, and its characteristics are well-known as shown in U.S. Pat. No. 4,459,577, etc. Metal oxide semiconductors such as BaSnO₃, CaSnO₃ and SrSnO₃, etc., are perovskite compounds and novel materials for exhaust gas sensors. Characteristics of these compounds are described in U.S. patent application No. 807,257 (Dec. 10, 1985) filed by the same assignee, and its descriptions will be cited hereinafter.

SUMMARY OF THE INVENTION

The object of the present invention is to prevent electrodes from corrosion due to the formation of an alloy of Pt and the metal element in a metal oxide semiconductor.

The exhaust gas sensor of this invention is characterized by combining a metal oxide semiconductor containing either one of elements,--Sn, Fe, Ni or Co--with Pt electrodes having ZrO₂ deposited in the crystalline grain boundaries.

Such metal oxide semiconductors include, for example, SnO₂, BaSnO₃, SrSnO₃, CaSnO₃. And other metal oxide semiconductors include SrFeO₃, LaNiO₃, LaCoO₃, La_(1-x) Sr_(x). Ni_(1-y) Co_(y) O₃, etc. These metal oxide semiconductors need not be used alone, but they can be used in mixtures with other metal oxide semiconductors, e.g., TiO₂, etc., or with a part of component elements substituted by other metal elements, or further, in mixtures of SnO₂, etc. with BaSnO₃, etc. It is, of course, permissible to add some known additives such as noble metal catalyzers, etc. to such semiconductors.

It is only necessary that the electrodes are mainly composed of Pt and ZrO₂ and are deposited in the crystal boundaries thereof. Those with such third components as Rh, Au, etc., added are also preferable.

The preferable amount of ZrO₂ is 0.01˜3.0 in weight % concentration and more preferably 0.1˜2.0.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of an exhaust gas sensor of the embodiment;

FIG. 2 is a plan view showing an exploded state of the exhaust gas sensor of the embodiment;

FIG. 3 is a characteristic graph showing corrosion resistance of the electrodes with respect to BaSnO₃ ;

FIG. 4 is a characteristic graph showing corrosion resistance of the electrodes with respect to SnO₂ ;

FIG. 5 is a characteristic graph showing corrosion resistance of the electrodes with respect to SrFeO₃ ;

FIG. 6 is a characteristic graph showing the corrosion resistance of the electrodes with respect to LaNiO₃ ; and

FIG. 7 is a characteristic graph showing the corrosion resistance of the electrodes with respect to LaCoO₃.

PREFERRED EMBODIMENTS

Manufacture of Exhaust Gas Sensors

(1) BaCO₃, SrCO₃ or CaCO₃ was mixed with SnO₂ in equimolar ratio to react them in air at 1200° C. for 4 hr, yielding a perovskite compound of BaSnO₃, SrSnO₃ or CaSnO₃. The compound thus obtained was pulverized and Pt electrodes with ZrO₂ (70 μin diameter, Tanaka Noble Metal Industry, Ltd.) available on the market were embedded therein, then was molded into a sensor chip shown in FIGS. 1 and 2. The chip thus molded was baked by heating in air at 1300° C. for 4 hours. The Pt electrode with ZrO₂ deposited in the crystal grain boundaries is hereinafter referred to as Pt-ZrO₂ electrode.

With the chip which has been sintered, an exhaust gas sensor (2) shown in FIGS. 1 and 2 was assembled. In these drawings, (4) denotes an insulating substrate of alumina, etc.; in the recess (6) provided at one end thereof, the sensor chip (8) is housed. Electrodes (10) and (12) on the chip (8) are housed in grooves (14) and (16) provided in the substrate (4), with their ends connected to base metal outside leads (18) and (20). Then an alumina sheet (22) is pasted on the substrate (4), leaving a gap along the circumferential rim of the chip (8), thereby shielding and protecting the electrodes (10) and (12) from the atmosphere. Any constructions of gas sensor (2) other than this can be employed as a matter of course.

(2) Similarly, Pt-ZrO₂ electrodes are connected with SnO₂ which has been calcined at 1200° C. and, then, this product is sintered at 1300° C., yielding a similar gas sensor (2).

(3) SrCO₃ and Fe₂ O₃ are mixed in equi-molar ratio. The mixture is, then, calcined in air at 1200° C. for 4 hr, yielding a perovskite compound SrFeO₃. This product is connected with Pt-ZrO₂ electrodes, similarly as in the case of (1), and is sintered at 1300° C., forming a sensor (2). Similarly, by reaction of lanthanum oxalate with NiO and that of lanthanum oxalate with CoO, a sensor (2) in which LaNiO₃ and LaCoO₃ are used are obtained. These manufacturing methods (1)˜(3) are equivalent, except for the semiconductors used.

(4) As comparative examples, the following sensors (2) are prepared:

(a) A sensor in which the Pt-ZrO₂ electrodes (10) and (12) are substituted by 80μ dia. Pt-Rh alloy electrodes (Rh 40% or 13% by weight).

(b) A sensor in which Pt (80μ dia.) with 1.0% by weight of TiO₂ deposited is used as the electrodes.

(c) A sensor in which Pt electrodes (70μ dia.) with 5% by weight of Au added are used.

(d) A sensor in which Pt-Rh alloy (Rh 40% by weight) is used as electrodes for TiO₂.

In these comparative examples, the manufacturing conditions of the sensor (2) are equivalent except for electrodes.

Characteristics of Semiconductors

SnO₂ is well-known as a material of exhaust gas sensors. On the other hand, BaSnO₃, SrSnO₃ and CaSnO₃ are novel as exhaust gas sensor materials; they are all perovskite compounds. BaSnO₃ is an n-type metal oxide semiconductor; its resistance value increases withair-fuel ratios in full range. SrSnO₃ and CaSnO₃ are compounds which have both the n- and p-type properties blended; thus, in a region (lean region) where the equivalent ratio λ is larger than 1, the resistance value diminishes with air-fuel ratios, thus showing the p-type property; while at the equivalent point (λ=1) or in rich region (a region in which λ is smaller than 1), the n-type property is apparent, with the resistance value increasing with air-fuel ratios.

Among these compounds, BaSnO₃ is most excellent. The oxygen sensitivity of BaSnO₃ is higher than those of SrSnO₃ or CaSnO₃. Oxygen sensitivities of BaSnO₃ and SnO₂ are on the same order, but BaSnO₃ is superior in its durability in reducing atmospheres and in the smaller detection errors due to unreacted inflammable gases in the exhaust gases. For example, when SnO₂ is exposed for a long time (4˜10 hr) to atmospheres with the equivalent ratios 0.9˜0.95 at 900° C., its resistance value irreversibly falls, but such a phenomenon does not occur with BaSnO₃. Then, SnO₂ shows high sensitivity to unreacted components (mainly CO and HC) in exhaust gases, but BaSnO₃ gives a low value. Because of the SnO₂ 's sensitivity to unreacted components being too high, as compared with that to oxygen, variations in the amounts of the unreacted components result in detection errors.

In the following, comparison results between BaSnO₃ and SnO₂ are cited from the description of U.S. patent application No. 807,257 (Table 1).

To the sample, 5 mol-% of SiO₂ (silica colloid) is added. Silica hardly exerts influence on durability in reducing atmospheres or the sensitivities to such inflammable gases as carbon monoxide, etc. The addition of silica increases the oxygen gradient of BaSnO₃ from 0.18 to 0.22. However, silica hardly affects the oxygen gradient of SnO₂.

It is evident that BaSnO₃ is superior to SnO₂ in the aspect of durability against the high temperature reducing atmosphere. Further, BaSnO₃ gives small detection error, when unreacted inflammable gases are remaining in the lean region. In Table 1, on the assumption of chemical equilibrium between carbon monoxide, and oxygen, the ratio of its resistance in 1,000 ppm CO to that in 10,000 ppm CO is 1.02, as calculated from the oxygen gradient. With BaSnO₃, by addition of a small amount of some noble metal catalyzer or by providing an oxidizing catalyzer layer outside the sensor, the error due to coexistence of inflammable gases may be eliminated. In contrast, with SnO₂, the detection error is large, CaSnO₃ or SrSnO₃ is superior to SnO₂ in the aspects of durability and small detection error due to inflammable gases.

                                      TABLE 1                                      __________________________________________________________________________     BaSnO.sub.3-δ vs. SnO.sub.2                                                             Reduction of                                                                   resistance due     Oxygen                                                      to endurance                                                                           CO sensitivity*.sup.2                                                                     gradient*.sup.3                              Specimen       test*.sup.1 (Rso/Rsf)                                                                  (R.sub.s co1000/R.sub.s co10,000)                                                         (at 700° C.)                          __________________________________________________________________________     BaSnO.sub.3-δ  + SiO.sub.2 5 mol %                                                      1.0     1.9        0.22                                         1400° C. baking                                                         BaSnO.sub.3-δ  + SiO.sub.2 5 mol %*.sup.4                                               1.0     1.02       0.22                                         1400° C. baking + Pt 100 ppm                                            SnO.sub.2 + SiO.sub.2 5 mol %                                                                 up to 10                                                                               up to 3    0.20                                         1400° C. baking                                                         SnO.sub.2 + SiO.sub.2 5 mol %                                                                 up to 10                                                                               up to 3    0.20                                         1400° C. baking + Pt 100 ppm                                            __________________________________________________________________________      *.sup.1 At 900° C. for 4 hours, the specimens are subjected to          repeated cycles of 4second periods including 3 seconds in an atmosophere       if λ = 0.8 and 1 second in an atmosphere of λ = 1.05 at          700° C. and checked for the resulting variation in resistance valu      to determine the ratio of the initial resistance value to the value after      the endurance test,                                                            *.sup.2 the ratio of the resistance value at 1,000 ppm of CO to that at        10,000 ppm of CO, as determined at 700° C. in a system containing       4.6% of oxygen and N.sub.2 in balance,                                         *.sup.3 the variation in the resistance value due to the change in O.sub.      concentration from 1% to 10%, as evaluated using Rs = K · P           · O.sub.2.sup.m,                                                      *.sup.4 the amount added of 1 μg per gram of the semiconductor is           expressed as 1 ppm.                                                      

Pt-ZrO₂ Electrodes

Pt-ZrO₂ electrodes (10) and (12) are ZrO₂ deposited Pt in its crystal grain boundaries. These electrodes are manufactured, for example, by mixing Pt powders with ZrO₂ powders and subjecting the mixture to hot forging in the way of powder metallurgy. The added ZrO₂ is segregated in the crystal grain boundaries and is hardly contained inside the Pt crystal as a solid solution. The formation of solid solution, and the diffusion of such elements as Sn, etc., into the electrode are presumed to proceed through the crystal boundaries of Pt. The formation of the solid solution of such elements as Sn, etc., is intercepted by depositing ZrO₂ in the grain boundaries.

With regard to the amount of ZrO₂ added, 0.01˜3.0% by weight is preferable; by using more than 0.01% by weight, sufficient corrosion resistance is achieved and by restraining it under 3.0% by weight, the hardness is restricted within a range conductive to easy machining. In this embodiment, the amount of ZrO₂ added was 0.6% by weight, but equivalent results were obtained with 0.3% by weight or 1.0% by weight. Accordingly, a more preferable amount of addition should be 0.1˜2% by weight. While in the embodiment, the electrode's wire diameter is set at 70 μ, arbitrary wire diameters may be chosen within a range where the electrode's proper mechanical strength may be assured, e.g., 50˜300 μ, or more preferably, 50˜200 μ. Further, Pt-Rh-ZrO₂ electrodes or Pt-Au-ZrO₂ electrodes etc., may be acceptable, if their main components are Pt.

Corrosion Resistance of Electrodes

For evaluation of electrodes for durability, the following tests are conducted with 6 each of gas sensors (2) of respective materials. Each sensor (2) is subjected to 20,000 cycles, one cycle being constituted by exposure to an atmosphere of 0.9λ at 900° C. and to air at 350° each for 90 sec, to a total of 3 min. The total time for the cycles amounts to 1,000 hr. Midway in the course of these cycles, the sensor (2) is examined for any wire disconnection by measurement of its resistance value and upon ending the cycles the electrodes are checked. The 0.9λ atmosphere is of a very strongly reducing nature as an atmosphere in which the gas sensors are placed and 900° C. corresponds to a maximum working temperature of gas sensors. Further, the temperature cycles at 350° C. and 900° C. impose a large thermal impact on the sensors. Accordingly, all these tests are rigorous in the aspects of atmosphere, maximum temperature and thermal impact.

FIG. 3 shows results obtained with BaSnO₃. In the case of samples 1˜6 in which a Pt-Rh alloy (Rh 40% weight) of 80μ wire diameter was used, even though containing large amount of Rh and having a large wire diameter, all sustained breaking of wires. On the other hand, a Pt-ZrO₂ alloy of Samples 7˜12 having a 70μ wire diameter and containing 0.6% by weight of ZrO₂, notwithstanding its diameter being small, did not sustain wire disconnection. It turned out from examination of the broken Pt-Rh alloy that Sn had diffused into the electrode interior to be alloyed therewith. On the other hand, in the Pt-ZrO₂ electrodes, Sn was existing merely in the surface part of the electrode as a solid solution of a low concentration , its diffusion being balked by ZrO₂ in the grain boundaries. FIG. 4 shows results of the same test conducted with SnO₂. Samples 1˜6 are prepared by using the aforementioned Pt-Rh alloy, while samples 7˜12 are formed with Pt-ZrO.sub. 2. The improvement in durability of electrodes by the use of Pt-ZrO₂ is commonly evident.

Test results with Sn base semiconductors are shown in Table 2:

                  TABLE 2                                                          ______________________________________                                         Durability of Electrodes (Sn base)                                                  Semiconductor and                                                                             Number                                                          additive to electrode                                                                         of wires   Cycles taken before                             No.  (wt %)*.sup.1  disconnected                                                                              wire*.sup.2 breaking                            ______________________________________                                         1*   BaSnO.sub.3                                                                             Rh40%     6/6      6,000                                         2*   BaSnO.sub.3                                                                             Rh13%     6/6                                                    3    BaSnO.sub.3                                                                             ZrO.sub.2 0.6%                                                                           0                                                      4*   SnO.sub.2                                                                               Rh40%     6/6      4,000                                         5    SnO.sub.2                                                                               ZrO.sub.2 0.6%                                                                           0                                                      6    SrSnO.sub.3                                                                             ZrO.sub.2 0.6%                                                                           0                                                      7*   CaSnO.sub.3                                                                             Au5%      5/6      8,000                                         8    CaSnO.sub.3                                                                             ZrO.sub.2 0.6%                                                                           0                                                      9*   SnO.sub.2                                                                               Pt--TiO.sub.2                                                                            4/6      13,000                                        10*  TiO.sub.2                                                                               Rh40%     0                                                      11   BaSnO.sub.3                                                                             ZrO.sub.2 0.3%                                                                           0                                                      12   BaSnO.sub.3                                                                             ZrO.sub.2 1.0%                                                                           0                                                      ______________________________________                                          *.sup.1 In all samples, the main component of the electrode is Pt and the      amount of the additive is given in % by weight concentration unit,             Pt--TiO.sub.2 indicates an electrode having TiO.sub.2 added at 1.0% by         weight concentration, the diameter of the electrode wire of Pt ZrO.sub.2       and Pt--Au is 70μ while that of others 80μ;                               *.sup.2 Average value of cycle numbers counted before wire disconnection      occurred to broken wires; and                                                  *identifies comparative examples.                                        

FIG. 5 gives results with SrFeO₃, FIG. 6 those with LaNiO₃, and FIG. 7 those with LaCoO₃. The measuring method used is similar to the case of BaSnO₃ and the enhancements in durability are similarly achieved with use of the Pt-ZrO₂ electrodes. And the corrosions similarly result from alloy formation from Pt with Fe, etc. These results are exhibited in Table 3, together with results to SrFeO₃ with Pt-TiO₂ electrodes.

                  TABLE 3                                                          ______________________________________                                         Durability of Electrodes (Fe, Ni and Co)                                            Semiconductor and          Cycles taken                                        additive to electrode                                                                        Number of wires                                                                             before wire*.sup.2                             No.  (wt %)*1      disconnected breaking                                       ______________________________________                                         1*   SrFeO.sub.3                                                                             Rh40%    6/6         5,000                                       2    SrFeO.sub.3                                                                             ZrO.sub.2                                                                               0                                                       3*   LaNiO.sub.3                                                                             Rh40%    4/6        13,000                                       4    LaNiO.sub.3                                                                             ZrO.sub.2                                                                               0                                                       5*   LaCoO.sub.3                                                                             Rh40%    3/6        13,000                                       6    LaCoO.sub.3                                                                             ZrO.sub.2                                                                               0                                                       7*   SrFeO.sub.3                                                                             Pt-TiO.sub.2                                                                            4/6        16,000                                       ______________________________________                                          *.sup.1 In all samples, the main component of the electrode is Pt and the      amount of the additive is given in % by weight concentration unit, in          addition, "ZrO.sub.2 " indicates an electrode having ZrO.sub.2 added at        0.6 wt % concentration, while Pt--TiO.sub.2 indicates an electrode having      TiO.sub.2 added at 1.0 wt % concentration, the diameter of the electrode       wire of Pt--ZrO.sub.2 is 70μ, while that of others 80μ;                  *.sup.2 Average value of cycle numbers counted before wire disconnection       occurred to broken wires; and                                                  *identifies comparative examples.                                        

In these embodiments, results with specified semiconductors are shown. The enhancement of durability by the use of Pt-ZrO₂ electrodes is similarly achieved, when the type of semiconductors and their conditions of preparation are altered. Corrosions result from alloying Pt with respective elements in the semiconductors - Sn, Fe, Ni and Co, so, even if LaCoO₃ is substituted by NdCoO₃, for example, the cause and mechanism of corrosion still remain unchanged. They are not changed by the choice of the starting material of the semiconductor or its baking conditions, either. 

What is claimed is:
 1. An exhaust gas sensor of the type comprising a metal oxide semiconductor which undergoes change in resistance value due to presence of gases, and at least one pair of electrodes connected with the metal oxide semiconductor, the improvement comprising the metal oxide semiconductor, containing at least one member of a group of elements consisting of Sn, Fe, Ni and Co, the main component of said electrodes being Pt or a platinum alloy, with ZrO₂ being deposited only in crystalline grain boundaries of the electrodes.
 2. An exhaust gas sensor as claimed in claim 1, wherein the metal oxide semiconductor is a perovskite compound ASnO₃ where A represents at least one member of a group of elements consisting of Ca, Sr and Ba.
 3. An exhaust gas sensor as claimed in claim 2, wherein the perovskite compound ASnO₃ is BaSnO₃.
 4. An exhaust gas sensor as claimed in claim 1, wherein the metal oxide semiconductor is a perovskite compound LnBO₃ where Ln represents at least one member of a group of elements consisting of lanthanides elements with atomic numbers 57 to 71 and alkaline earth elements, and B represents at least one member of a group of elements consisting of Fe, Ni and Co.
 5. An exhaust gas sensor as claimed in claim 4, wherein the perovskite compound LnBo₃ denotes at least one member of a group of compounds consisting of SrFeO₃, LaNiO₃ and LaCoO₃.
 6. An exhaust gas sensor as claimed in claim 1, wherein the ZrO₂ content in the electrodes is 0.01 to 3% by weight.
 7. An exhaust gas sensor as claimed in claim 6, wherein the ZrO₂ content in the electrodes is 0.1 to 2% by weight.
 8. The exhaust gas sensor of claim 1 wherein the main component of said electrodes is Pt.
 9. The exhaust gas sensor of claim 1 wherein the main component of said electrodes is a Pt alloy such as Pt-Rh or Pt-Au. 